US11801494B2 - Method for preparing single-atom catalyst supported on carbon support - Google Patents
Method for preparing single-atom catalyst supported on carbon support Download PDFInfo
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- US11801494B2 US11801494B2 US17/271,206 US201917271206A US11801494B2 US 11801494 B2 US11801494 B2 US 11801494B2 US 201917271206 A US201917271206 A US 201917271206A US 11801494 B2 US11801494 B2 US 11801494B2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 148
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000002243 precursor Substances 0.000 claims abstract description 78
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 16
- 239000012808 vapor phase Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 124
- 229910052757 nitrogen Inorganic materials 0.000 claims description 62
- 229910017052 cobalt Inorganic materials 0.000 claims description 55
- 239000010941 cobalt Substances 0.000 claims description 55
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 55
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- 239000010948 rhodium Substances 0.000 claims description 25
- 229910052755 nonmetal Inorganic materials 0.000 claims description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 17
- 229910052796 boron Inorganic materials 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 16
- 239000011669 selenium Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 229910052703 rhodium Inorganic materials 0.000 claims description 13
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 12
- 229910052741 iridium Inorganic materials 0.000 claims description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- 229910052768 actinide Inorganic materials 0.000 claims description 4
- 150000001255 actinides Chemical class 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052713 technetium Inorganic materials 0.000 claims description 4
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical compound C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021640 Iridium dichloride Inorganic materials 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 238000001947 vapour-phase growth Methods 0.000 claims description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
- 229910019131 CoBr2 Inorganic materials 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910003472 fullerene Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 239000011147 inorganic material Substances 0.000 claims description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 2
- 239000002127 nanobelt Substances 0.000 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000004549 pulsed laser deposition Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 claims description 2
- 238000010891 electric arc Methods 0.000 claims 4
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 125000004429 atom Chemical group 0.000 description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000004502 linear sweep voltammetry Methods 0.000 description 8
- 239000002116 nanohorn Substances 0.000 description 8
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- 239000007789 gas Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- 238000004627 transmission electron microscopy Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910020676 Co—N Inorganic materials 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 239000010970 precious metal Substances 0.000 description 1
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- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/347—Ionic or cathodic spraying; Electric discharge
Definitions
- the disclosure relates to a method for manufacturing a single-atom catalyst supported on a carbon support.
- Metal-supported catalysts are widely used in various industrial fields due to their high activity, selectivity, and stability, and in order to maximize the use of precious metals, studies have been conducted to highly disperse metals in a small size.
- single-atom-sized metal catalysts exhibit different catalytic activities due to different electrical properties from general metal catalysts as well as high metal dispersion. Further, such catalysts may maximize catalytic activities, and exhibit high chemoselectivity due to extremely limited active sites compared to catalysts having metal clusters with multiple active sites, and thus are attracting great attention.
- single-atom-sized metals are quite unstable due to a tendency to agglomerate in order to maximize their surface energy. Therefore, single-atom-sized metal catalysts may be synthesized only when catalyst supports having strong bonds with metals to stabilize the metals even in a single atom size are used.
- the catalyst supports having strong bonds with metals to stabilize the metals even in a single atom size are mostly insulators or ceramics. Since such insulators or ceramic supports have excellent mechanical strength, in order to introduce metal atoms, a top-down approach has been used to introduce strong energy (e.g., using ball mill) after adsorbing metal atoms.
- insulators or ceramic supports have low electrical conductivity and are unstable under electrochemical conditions, and thus, it is almost impossible to apply the single-atom-sized metal catalysts supported on such supports to an electrochemical reaction. Therefore, there is a need for catalyst supports capable of stabilizing metals even in a single atom size while having high electrical conductivity.
- An aspect is to provide a method for manufacturing a single-atom catalyst supported on a carbon support.
- a method for manufacturing a single-atom catalyst supported on a carbon support including: treating a mixture of a precursor of a carbon support and a precursor of a hetero element other than carbon through a dry vapor phase process to support, on a carbon support, a single-atom catalyst containing a hetero element other than carbon.
- a method for manufacturing a single-atom catalyst supported on a carbon support may, through a bottom-up approach, introduce a single-atom catalyst material into a carbon lattice when generating a carbon support, thereby manufacturing a single-atom catalyst supported on a carbon support having high crystallinity and a large specific surface area.
- the single-atom catalyst supported on the carbon support has excellent electrical conductivity, and has excellent catalytic activity and selectivity as the single-atom catalyst is evenly dispersed on the carbon support.
- FIG. 1 is results of X-ray diffraction (XRD) of a carbon structure doped with nitrogen (N) of Example 1 and a carbon structure doped with cobalt (Co) and nitrogen (N) together of Example 2.
- XRD X-ray diffraction
- FIG. 2 is results of scanning electron microscopy (SEM) of (a) a carbon structure doped with nitrogen (N) of Example 1 and (b) a carbon structure doped with cobalt (Co) and nitrogen (N) together of Example 2.
- FIG. 3 is results of transmission electron microscopy (TEM) of (a) a carbon structure doped with nitrogen (N) of Example 1 and (b) a carbon structure doped with cobalt (Co) and nitrogen (N) together of Example 2.
- TEM transmission electron microscopy
- FIG. 4 is results of X-ray photoelectron spectroscopy (XPS) analysis for examining binding properties of cobalt to a carbon structure doped with cobalt and nitrogen together of Example 13.
- XPS X-ray photoelectron spectroscopy
- FIG. 5 is results of XPS analysis according to with/without ammonia heat treatment and temperature of the carbon structure doped with cobalt and nitrogen together of Example 13.
- FIGS. 6 A to 6 C are linear sweep voltammetry (LSV) measurement results showing the catalytic activity of the carbon structure doped with cobalt and nitrogen together of Example 13.
- FIG. 7 is a graph of LSV results of measuring catalytic activity changes according to the amount of a cobalt element for the carbon structure doped with cobalt and nitrogen together of Example 13.
- FIG. 8 is a graph of LSV results according to ammonia heat treatment temperature for the carbon structure doped with cobalt and nitrogen together of Example 13.
- FIG. 9 is an LSV result graph showing catalytic activity life characteristics according to the number of redox cycles for the carbon structure doped with cobalt and nitrogen together of Example 13.
- the method for manufacturing a single-atom catalyst supported on a carbon support includes treating a mixture of a precursor of a carbon support and a precursor of a hetero element other than carbon through a dry vapor phase process to support, on a carbon support, a single-atom catalyst containing a hetero element other than carbon.
- hetero elements are evenly dispersed in the form of a single atom on a carbon support to manufacture a supported catalyst.
- the method for manufacturing a single-atom catalyst supported on a carbon support according to the disclosure is characterized in that a catalyst material is introduced into a carbon lattice in the form of a single atom in the manufacturing of a carbon support having high crystallinity.
- the method for manufacturing a single-atom catalyst supported on a carbon support according to the disclosure is based on a bottom-up approach, which allows a carbon support having high crystallinity and a large specific surface area to be manufactured.
- a carbon support has reduced electrical conductivity due to high chances of a crystal structure of the carbon support being destroyed to cause a decrease in crystallinity.
- the catalyst material is evenly dispersed in the form of a single atom on the carbon support to generate a supported catalyst, thereby providing excellent catalytic activity and selectivity.
- the precursor of the carbon support refers to a raw material of the carbon support, and may be selected from, for example, graphite, C 2 H 2 , CH 4 , C 2 H 4 , C 2 H 6 , and C 2 H 5 OH, but is not limited thereto, and may include one type alone or two or more types.
- graphite when performing are discharge according to an embodiment of the disclosure, graphite may be used, and when using vapor phase growth, C 2 H 2 , CH 4 , C 2 H 4 , C 2 H 6 , etc. may be used.
- the hetero element of the hetero element precursor refers to a single-atom hetero element other than carbon, supported on a carbon support, and may include, for example, a non-metal, a metal other than carbon, or a combination thereof.
- the hetero element of the hetero element precursor may include at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); at least one metal selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, La, Zr, Hf, Nb, Ta, Mo, W, Tc, Re, Ru, Os, Rh, Ir, Pd, of Pt, Ag, Au, Cd, Hg, Ga, Ge, In, Sn, Sb, Tl, Pb, Bi, lanthanides, and actinides; or a combination thereof.
- the precursor of the hetero element other than carbon may include at least one non-metal-containing precursor containing at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), and phosphorus (P); at least one metal-containing precursor containing at least one metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Ru, Rh, Ir, Pd, Pt, Ag, Au, Cd, Ga, Ge, In, Sn, Sb, and Tl; or a combination thereof.
- the hetero element of the hetero element precursor may include at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); at least one metal among cobalt (Co), iron (Fe), nickel (Ni), rhodium (Rh), and iridium (Ir); or a combination thereof.
- the hetero element of the hetero element precursor may include nitrogen (N), cobalt (Co), or a combination thereof.
- the hetero element of the hetero element precursor may include nitrogen (N) and cobalt (Co) together.
- the hetero element of the hetero element precursor may include nitrogen (N) or cobalt (Co).
- the precursor of the hetero element refers to a raw material of a hetero element supported on a carbon support.
- the precursor of the hetero element may include at least one non-metal-containing precursor containing at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); at least one metal-containing precursor containing at least one metal selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, La, Zr, Hf, Nb, Ta, Mo, W, Tc, Re, Ru, Os, Rh, Ir, Pd, of Pt, Ag, Au, Cd, Hg, Ga, Ge, In, Sn, Sb, Tl, Pb, Bi, lanthanides, and actinides; or a combination thereof.
- the precursor of the hetero element may include at least one non-metal-containing precursor containing at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); at least one transition metal-containing precursor containing at least one transition metal selected from cobalt (Co), iron (Fe), nickel (Ni), rhodium (Rh), and iridium (Ir); or a combination thereof.
- non-metal-containing precursor containing at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); at least one transition metal-containing precursor containing at least one transition metal selected from cobalt (Co), iron (Fe), nickel (Ni), rhodium (Rh),
- the nitrogen-containing precursor may include at least one selected from N 2 , NH 3 , N 2 H 4 , R x NH 3-x (R is a C 1 to C 6 alkyl group, and x is 1 or 2), R x N 2 H 4-x (R is a C 1 to C 6 alkyl group, and x is an integer of 3 or less), a solid inorganic material containing a nitrogen element, and a nitrogen element-containing polymer, but is not limited thereto.
- the metal-containing precursor may include CoCl 2 , CoBr 2 , Co(NO 3 ) 2 , Co(OH) 2 , Co(CH 3 COO) 2 , FeCl 2 , FeBr 2 , Fe(NO 3 ) 2 , Fe(OH) 2 , Fe(CH 3 COO) 2 , NiCl 2 , NiBr 2 , Ni(NO 3 ) 2 , Ni(OH) 2 , Ni(CH 3 COO) 2 , RhCl 2 , RhBr 2 , Rh(NO 3 ) 2 , Rh(OH) 2 , Rh(CH 3 COO) 2 , IrCl 2 , IrBr 2 , Ir(NO 3 ) 2 , Ir(OH) 2 , Ir(CH 3 COO) 2 , etc., but is not necessarily limited thereto, and may include one type alone or two or more types.
- CoCl 2 may be used as a precursor of cobalt (Co), but it is not
- the amount of the precursor of the hetero element in the mixture may be about 0.01% by weight to about 10% by weight with respect to the total weight of the precursor of the carbon support.
- the amount of the precursor of the hetero element in the mixture may be about 0.05% by weight to about 8% by weight with respect to the total weight of the precursor of the carbon support.
- the amount of the precursor of the hetero element in the mixture may be about 0.1% by weight to about 5% by weight with respect to the total weight of the precursor of the carbon support.
- the amount of the precursor of the hetero element in the mixture may be about 0.2% by weight to about 4% by weight with respect to the total weight of the precursor of the carbon support.
- the mixture of the precursor of the carbon support and the precursor of the hetero element may be a solid, a liquid, a gas, or a mixture thereof.
- the mixture of the precursor of the carbon support and the precursor of the hetero element may be in a mixed state of a solid and a gas.
- the mixture of the precursor of the carbon support and the precursor of the hetero element may be in a mixed state of a solid and a gas.
- alcohol e.g., ethanol
- water may be used as a solvent, but is not limited thereto.
- the solvent may be used alone or in combination of two or more.
- carbon support growth used in the method for manufacturing a single-atom catalyst supported on a carbon support is not particularly limited as long as the process used therein is a dry vapor phase process.
- the dry vapor phase process may be performed through at least one process among are discharge, thermal chemical vapor deposition, plasma synthesis, high-temperature plasma, plasma-enhanced chemical vapor deposition, laser evaporation, laser ablation, and vapor phase growth.
- the dry vapor phase process may be performed through are discharge.
- the are discharge may be performed at a voltage of about 10 V to about 50 V.
- the are discharge may be performed at a voltage of about 20 V to about 40 V.
- the are discharge may be performed at a voltage of about 25 V to about 35 V.
- the are discharge may be performed at a current of about 50 A to about 300 A.
- the are discharge may be performed at a current of about 100 A to about 200 A.
- the are discharge may be performed at a current of about 150 A to about 200 A.
- a dry vapor phase process may be performed in a gas atmosphere of a non-metal-containing precursor.
- are discharge may be performed in a gas atmosphere of a non-metal-containing precursor. For example, when a reaction chamber is filled with a nitrogen-containing gas and then precursor powder of a carbon support is arc-discharged, nitrogen (N) may be evenly dispersed at the level of a single atom on the generated carbon support.
- nitrogen (N) and a transition metal may be evenly dispersed at the level of a single atom on the generated carbon support.
- the single-atom catalyst supported on the carbon support manufactured by the method above may include a carbon support and a single-atom catalyst dispersed on the support.
- the single-atom catalyst refers to a catalyst in the form that a single atom, which is the smallest in size that a catalyst material has, is dispersed on a support.
- the single-atom catalyst supported on the carbon support is characterized in that a catalyst material containing a hetero element other than carbon is evenly dispersed at the level of a single atom on a carbon support having excellent electrical conductivity. The characteristics allow the single-atom catalyst supported on the carbon support to have excellent electrical conductivity compared to a conventional nano-sized catalyst, and to have excellent catalytic activity and selectivity.
- the carbon support refers to a carbon-based material having a large specific surface area and high crystallinity.
- the carbon support may include graphene, graphene oxide, fullerene, carbon nanotubes (CNT), carbon nanofibers, carbon nanobelts, carbon nanoonions, carbon nanohorns, activated carbon, graphite, etc., but is not necessarily limited thereto, and any carbon supports that may be used as a carbon support in the art are all applicable.
- the carbon support may have a structure such as a spherical shape, a rod shape, a tube shape, a horn shape, and a plate shape, but is not necessarily limited to such structures, and any structures that may be used as a carbon support in the art are all applicable.
- the carbon support may be a porous carbon material having a large specific surface area and pores.
- the carbon support is a nanohorn having a horn-shaped structure.
- the carbon support may be porous.
- the carbon support may be mesoporous.
- some or all of the various types of carbon supports described above may be porous.
- the carbon support may have an average diameter of about 1 nm to about 10 ⁇ m.
- the carbon support may have an average diameter of about 10 nm to about 5 ⁇ m.
- the carbon support may have an average diameter of about 100 nm to about 1 ⁇ m.
- the carbon support may have an average diameter of about 200 nm to about 500 nm.
- the catalyst may be evenly dispersed in the form of a single atom on the carbon support, and catalytic activity and selectivity are excellent.
- single-atom catalyst indicates that a catalyst material is dispersed as single-atom units together and evenly supported on a carbon support, and the single-atom catalyst is distinct from nanoparticles or microparticles formed of agglomerated catalyst materials, which are supported on a carbon support.
- the catalyst material is dispersed as single atom units together on a carbon support, and thus, the catalyst has excellent activity and selectivity.
- the single-atom catalyst may include all hetero elements other than carbon.
- the single-atom catalyst may include a non-metal, a metal other than carbon, or a combination thereof.
- the single-atom catalyst may include at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); a transition metal; or a combination thereof.
- the single-atom catalyst may include at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); at least one transition metal selected from cobalt (Co), iron (Fe), nickel (Ni), rhodium (Rh), and iridium (Ir); or a combination thereof.
- the single-atom catalyst may include nitrogen (N), cobalt (Co), or a combination thereof.
- the single-atom catalyst may include nitrogen (N) and cobalt (Co) together.
- the single-atom catalyst may include nitrogen (N) or cobalt (Co).
- the supported amount of the single-atom catalyst may be about 0.01% by weight to about 10% by weight with respect to the total weight of the carbon support.
- the supported amount of the single-atom catalyst may be about 0.05% by weight to about 8% by weight with respect to the total weight of the carbon support.
- the supported amount of the single-atom catalyst may be about 1% by weight to about 5% by weight with respect to the total weight of the carbon support.
- the supported amount of the single-atom catalyst may be about 2% by weight to about 4% by weight with respect to the total weight of the carbon support.
- the single-atom catalyst supported on the carbon support has excellent electrical conductivity and excellent catalytic activity and selectivity, and accordingly, the single-atom catalyst may be used in electrochemical or chemical reaction fields where conventional nano-sized or micro-sized catalysts are not applicable or hard to be applicable.
- the single-atom catalyst may be used for fuel cells, highly sensitive biosensors, or chemical conversion reactions.
- the negative electrode was introduced into a reaction chamber, and the chamber was charged with a nitrogen atmosphere, and then a voltage of 30 V and a current of 150 A were applied thereto for 5 minutes to generate an intense arc.
- the product was cooled and washed with ethanol to manufacture a carbon structure doped with nitrogen (N).
- Example 2 Cobalt (Co) and Nitrogen (N) Single Atoms Supported Together on a Carbon Support
- CoCl 2 0.1 g was mixed with ethanol, and then 100 g of graphite powder was added to the mixture and stirred. Thereafter, the mixed solution was dried in an oven at 50° C. for 2 hours to completely evaporate the solvent to manufacture composite powder having CoCl 2 adsorbed on a surface of the graphite.
- the obtained composite powder was fully filled in a cylindrical negative electrode with an empty center, and then sufficiently dried in an oven to remove moisture.
- the negative electrode was introduced into a reaction chamber, and the chamber was charged with a nitrogen atmosphere, and then a voltage of 30 V and a current of 150 A were applied thereto for 5 minutes to generate an intense arc.
- the product was cooled and washed with ethanol to manufacture a carbon structure doped with cobalt (Co) and nitrogen (N) together.
- Example 3 Cobalt (Co) Single Atom Supported on a Carbon Support
- a carbon structure doped with cobalt (Co) was manufactured in the same manner as in Example 2, except that a hydrogen atmosphere was applied instead of a nitrogen atmosphere.
- a carbon structure doped with iron (Fe) was manufactured in the same manner as in Example 2, except that a hydrogen atmosphere was applied instead of a nitrogen atmosphere, and FeCl 2 was used instead of CoCl 2 .
- Example 5 Nickel (Ni) Single Atom Supported on a Carbon Support
- a carbon structure doped with nickel (Ni) was manufactured in the same manner as in Example 2, except that a hydrogen atmosphere was applied instead of a nitrogen atmosphere, and NiCl 2 was used instead of COCl 2 .
- a carbon structure doped with rhodium (Rh) was manufactured in the same manner as in Example 2, except that a hydrogen atmosphere was applied instead of a nitrogen atmosphere, and RhCl 2 was used instead of CoCl 2 .
- Example 7 Iridium (Ir) Single Atom Supported on a Carbon Support
- a carbon structure doped with iridium (Ir) was manufactured in the same manner as in Example 2, except that a hydrogen atmosphere was applied instead of a nitrogen atmosphere, and IrCl 2 was used instead of CoCl 2 .
- Example 8 Boron (B) Single Atom Supported on a Carbon Support
- a carbon structure doped with boron (B) was manufactured in the same manner as in Example 1, except that a boron atmosphere was applied instead of a nitrogen atmosphere.
- a carbon structure doped with sulfur (S) was manufactured in the same manner as in Example 1, except that a sulfur atmosphere was applied instead of a nitrogen atmosphere.
- Example 10 Phosphorus (P) Single Atom Supported on a Carbon Support
- a carbon structure doped with phosphorus (P) was manufactured in the same manner as in Example 1, except that a phosphorus atmosphere was applied instead of a nitrogen atmosphere.
- Example 11 Nickel (Ni) and Boron (B) Single Atoms Supported Together on a Carbon Support
- a carbon structure doped with nickel (Ni) and boron (B) together was manufactured in the same manner as in Example 2, except that a boron atmosphere was applied instead of a nitrogen atmosphere, and NiCl 2 was used instead of CoCl 2 .
- Example 12 Cobalt (Co), Nickel (Ni) and Nitrogen (N) Single Atoms Supported Together on a Carbon Support
- a carbon structure doped with cobalt (Co), nickel (Ni) and nitrogen (N) together was manufactured in the same manner as in Example 2, except that a mixture of CoCl 2 and NiCl 2 was used instead of CoCl 2 .
- X-ray diffraction (XRD) analysis was performed on the carbon structure doped with nitrogen (N) of Example 1 and the carbon structure doped with cobalt (Co) and nitrogen (N) together of Example 2, and the results are shown in FIG. 1 .
- the XRD results of the carbon structures of Examples 1 and 2 showed a sharp 2 ⁇ diffraction peak at about 25°, indicating that the carbon structure was a crystalline structure. However, no peaks resulting from nitrogen (N) and cobalt (Co) were observed, indicating that nitrogen (N) and cobalt (Co) each were doped to the carbon structure at the level of a single atom rather than a large nanoparticle.
- SEM scanning electron microscopy
- TEM transmission electron microscopy
- the carbon nanohorn had an average diameter of about 20 nm to about 50 nm.
- Composite powder having different amounts of CoCl 2 adsorbed on a surface of graphite was manufactured by applying different amounts of a metal precursor mixed with graphite from low to high concentrations.
- the obtained composite powder was filled in a cylindrical negative electrode with an empty center, and then dried in an oven to remove moisture.
- the negative electrode was introduced into a reaction chamber, and the chamber was charged with a nitrogen atmosphere, and then a voltage of 30 V and a current of 150 A were applied thereto for 5 minutes to generate an intense arc.
- the product was cooled and washed with ethanol to manufacture a carbon structure doped with various amounts of cobalt (Co) and nitrogen (N) together.
- X-ray photoelectron spectroscopy (XPS) analysis was performed to examine binding properties of cobalt for the carbon structure doped with cobalt and nitrogen together of Example 13, and the results are shown in FIG. 4 . As shown in FIG. 4 , it was found that, with an increase in the amount of the cobalt element, Co—N bonds were observed, indicating that more bonds between cobalt and nitrogen were generated.
- XPS X-ray photoelectron spectroscopy
- FIG. 7 shows a graph of the LSV results of measuring catalytic activity changes according to the amount of a cobalt element.
- FIG. 7 shows a graph of the LSV results of measuring catalytic activity changes according to the amount of a cobalt element.
- FIG. 8 shows a graph of the LSV results according to ammonia heat treatment temperature.
- the increase in the activity up to 700° C. at the ammonia heat treatment temperature indicates that a cobalt single atom stably forms a coordination structure
- the decrease in activity from 800° C. indicates that the carbon structure collapses.
- FIG. 9 shows a graph of LSV results showing catalytic activity life characteristics according to the number of redox cycles. As shown in FIG. 9 , it was found that the manufactured single-atom catalyst has excellent stability, and the manufactured single-atom catalyst works quite stably even after 10,000 or more cycles.
- a method for manufacturing a single-atom catalyst supported on a carbon support through a bottom-up approach, introduces a single-atom catalyst material into a carbon lattice when generating a carbon support, thereby manufacturing a single-atom catalyst supported on a carbon support having high crystallinity and a large specific surface area.
- the single-atom catalyst supported on the carbon support has excellent electrical conductivity, and has excellent catalytic activity and selectivity as the single-atom catalyst is evenly dispersed on the carbon support.
Abstract
Provided is a method for manufacturing a single-atom catalyst supported on a carbon support, including treating a mixture of a precursor of a carbon support and a precursor of a hetero element other than carbon through a dry vapor phase process, thereby supporting, on a carbon support, a single-atom catalyst containing a hetero element other than carbon.
Description
The disclosure relates to a method for manufacturing a single-atom catalyst supported on a carbon support.
Metal-supported catalysts are widely used in various industrial fields due to their high activity, selectivity, and stability, and in order to maximize the use of precious metals, studies have been conducted to highly disperse metals in a small size.
In particular, single-atom-sized metal catalysts exhibit different catalytic activities due to different electrical properties from general metal catalysts as well as high metal dispersion. Further, such catalysts may maximize catalytic activities, and exhibit high chemoselectivity due to extremely limited active sites compared to catalysts having metal clusters with multiple active sites, and thus are attracting great attention.
However, single-atom-sized metals are quite unstable due to a tendency to agglomerate in order to maximize their surface energy. Therefore, single-atom-sized metal catalysts may be synthesized only when catalyst supports having strong bonds with metals to stabilize the metals even in a single atom size are used. The catalyst supports having strong bonds with metals to stabilize the metals even in a single atom size are mostly insulators or ceramics. Since such insulators or ceramic supports have excellent mechanical strength, in order to introduce metal atoms, a top-down approach has been used to introduce strong energy (e.g., using ball mill) after adsorbing metal atoms. However, insulators or ceramic supports have low electrical conductivity and are unstable under electrochemical conditions, and thus, it is almost impossible to apply the single-atom-sized metal catalysts supported on such supports to an electrochemical reaction. Therefore, there is a need for catalyst supports capable of stabilizing metals even in a single atom size while having high electrical conductivity.
An aspect is to provide a method for manufacturing a single-atom catalyst supported on a carbon support.
According to an aspect,
there is provided a method for manufacturing a single-atom catalyst supported on a carbon support, including: treating a mixture of a precursor of a carbon support and a precursor of a hetero element other than carbon through a dry vapor phase process to support, on a carbon support, a single-atom catalyst containing a hetero element other than carbon.
According to an aspect, a method for manufacturing a single-atom catalyst supported on a carbon support may, through a bottom-up approach, introduce a single-atom catalyst material into a carbon lattice when generating a carbon support, thereby manufacturing a single-atom catalyst supported on a carbon support having high crystallinity and a large specific surface area.
The single-atom catalyst supported on the carbon support has excellent electrical conductivity, and has excellent catalytic activity and selectivity as the single-atom catalyst is evenly dispersed on the carbon support.
Hereinafter, a method for manufacturing a single-atom catalyst supported on a carbon support according to example embodiments will be explained in more detail.
The method for manufacturing a single-atom catalyst supported on a carbon support according to an embodiment includes treating a mixture of a precursor of a carbon support and a precursor of a hetero element other than carbon through a dry vapor phase process to support, on a carbon support, a single-atom catalyst containing a hetero element other than carbon.
According to the manufacturing method of the disclosure as described above, hetero elements are evenly dispersed in the form of a single atom on a carbon support to manufacture a supported catalyst.
The method for manufacturing a single-atom catalyst supported on a carbon support according to the disclosure is characterized in that a catalyst material is introduced into a carbon lattice in the form of a single atom in the manufacturing of a carbon support having high crystallinity.
The method for manufacturing a single-atom catalyst supported on a carbon support according to the disclosure is based on a bottom-up approach, which allows a carbon support having high crystallinity and a large specific surface area to be manufactured. When a conventional top-down approach is applied, there is a limitation that a carbon support has reduced electrical conductivity due to high chances of a crystal structure of the carbon support being destroyed to cause a decrease in crystallinity.
According to the manufacturing method of the disclosure as described above, the catalyst material is evenly dispersed in the form of a single atom on the carbon support to generate a supported catalyst, thereby providing excellent catalytic activity and selectivity.
The precursor of the carbon support refers to a raw material of the carbon support, and may be selected from, for example, graphite, C2H2, CH4, C2H4, C2H6, and C2H5OH, but is not limited thereto, and may include one type alone or two or more types.
For example, when performing are discharge according to an embodiment of the disclosure, graphite may be used, and when using vapor phase growth, C2H2, CH4, C2H4, C2H6, etc. may be used.
The hetero element of the hetero element precursor refers to a single-atom hetero element other than carbon, supported on a carbon support, and may include, for example, a non-metal, a metal other than carbon, or a combination thereof. For example, the hetero element of the hetero element precursor may include at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); at least one metal selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, La, Zr, Hf, Nb, Ta, Mo, W, Tc, Re, Ru, Os, Rh, Ir, Pd, of Pt, Ag, Au, Cd, Hg, Ga, Ge, In, Sn, Sb, Tl, Pb, Bi, lanthanides, and actinides; or a combination thereof. For example, the precursor of the hetero element other than carbon may include at least one non-metal-containing precursor containing at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), and phosphorus (P); at least one metal-containing precursor containing at least one metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Ru, Rh, Ir, Pd, Pt, Ag, Au, Cd, Ga, Ge, In, Sn, Sb, and Tl; or a combination thereof. For example, the hetero element of the hetero element precursor may include at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); at least one metal among cobalt (Co), iron (Fe), nickel (Ni), rhodium (Rh), and iridium (Ir); or a combination thereof. For example, the hetero element of the hetero element precursor may include nitrogen (N), cobalt (Co), or a combination thereof. For example, the hetero element of the hetero element precursor may include nitrogen (N) and cobalt (Co) together. For example, the hetero element of the hetero element precursor may include nitrogen (N) or cobalt (Co).
The precursor of the hetero element refers to a raw material of a hetero element supported on a carbon support. For example, the precursor of the hetero element may include at least one non-metal-containing precursor containing at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); at least one metal-containing precursor containing at least one metal selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, La, Zr, Hf, Nb, Ta, Mo, W, Tc, Re, Ru, Os, Rh, Ir, Pd, of Pt, Ag, Au, Cd, Hg, Ga, Ge, In, Sn, Sb, Tl, Pb, Bi, lanthanides, and actinides; or a combination thereof. For example, the precursor of the hetero element may include at least one non-metal-containing precursor containing at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); at least one transition metal-containing precursor containing at least one transition metal selected from cobalt (Co), iron (Fe), nickel (Ni), rhodium (Rh), and iridium (Ir); or a combination thereof.
According to an embodiment, the nitrogen-containing precursor may include at least one selected from N2, NH3, N2H4, RxNH3-x (R is a C1 to C6 alkyl group, and x is 1 or 2), RxN2H4-x (R is a C1 to C6 alkyl group, and x is an integer of 3 or less), a solid inorganic material containing a nitrogen element, and a nitrogen element-containing polymer, but is not limited thereto.
According to an embodiment, the metal-containing precursor may include CoCl2, CoBr2, Co(NO3)2, Co(OH)2, Co(CH3COO)2, FeCl2, FeBr2, Fe(NO3)2, Fe(OH)2, Fe(CH3COO)2, NiCl2, NiBr2, Ni(NO3)2, Ni(OH)2, Ni(CH3COO)2, RhCl2, RhBr2, Rh(NO3)2, Rh(OH)2, Rh(CH3COO)2, IrCl2, IrBr2, Ir(NO3)2, Ir(OH)2, Ir(CH3COO)2, etc., but is not necessarily limited thereto, and may include one type alone or two or more types. For example, CoCl2 may be used as a precursor of cobalt (Co), but it is not necessarily limited thereto, and all metal precursors other than carbon are applicable as long as the purpose is to have the precursors supported on a carbon carrier.
The amount of the precursor of the hetero element in the mixture may be about 0.01% by weight to about 10% by weight with respect to the total weight of the precursor of the carbon support. For example, the amount of the precursor of the hetero element in the mixture may be about 0.05% by weight to about 8% by weight with respect to the total weight of the precursor of the carbon support. For example, the amount of the precursor of the hetero element in the mixture may be about 0.1% by weight to about 5% by weight with respect to the total weight of the precursor of the carbon support. For example, the amount of the precursor of the hetero element in the mixture may be about 0.2% by weight to about 4% by weight with respect to the total weight of the precursor of the carbon support. When the amount of the precursor of the hetero element in the mixture is within the above range, the hetero element may be evenly dispersed in the form of a single atom on the carbon support, and accordingly, catalytic activity and selectivity may be excellent.
The mixture of the precursor of the carbon support and the precursor of the hetero element may be a solid, a liquid, a gas, or a mixture thereof. For example, the mixture of the precursor of the carbon support and the precursor of the hetero element may be in a mixed state of a solid and a gas. For example, the mixture of the precursor of the carbon support and the precursor of the hetero element may be in a mixed state of a solid and a gas. When the mixture is in a liquid state, alcohol (e.g., ethanol) or water may be used as a solvent, but is not limited thereto. The solvent may be used alone or in combination of two or more.
According to an embodiment of the disclosure, carbon support growth used in the method for manufacturing a single-atom catalyst supported on a carbon support is not particularly limited as long as the process used therein is a dry vapor phase process.
According to an embodiment, the dry vapor phase process may be performed through at least one process among are discharge, thermal chemical vapor deposition, plasma synthesis, high-temperature plasma, plasma-enhanced chemical vapor deposition, laser evaporation, laser ablation, and vapor phase growth.
According to an embodiment, the dry vapor phase process may be performed through are discharge.
The are discharge may be performed at a voltage of about 10 V to about 50 V. For example, the are discharge may be performed at a voltage of about 20 V to about 40 V. For example, the are discharge may be performed at a voltage of about 25 V to about 35 V. The are discharge may be performed at a current of about 50 A to about 300 A. For example, the are discharge may be performed at a current of about 100 A to about 200 A. For example, the are discharge may be performed at a current of about 150 A to about 200 A. When the voltage and current of the are discharge are controlled within the above range, the single-atom catalyst is evenly dispersed on the carbon support to manufacture a supported catalyst.
According to an embodiment, in the method for manufacturing a single-atom catalyst supported on a carbon support, a dry vapor phase process may be performed in a gas atmosphere of a non-metal-containing precursor. According to an embodiment, in the method for manufacturing a single-atom catalyst supported on a carbon support, are discharge may be performed in a gas atmosphere of a non-metal-containing precursor. For example, when a reaction chamber is filled with a nitrogen-containing gas and then precursor powder of a carbon support is arc-discharged, nitrogen (N) may be evenly dispersed at the level of a single atom on the generated carbon support. For example, when a reaction chamber is filled with a nitrogen-containing gas, and then mixed powder of a carbon support precursor and a transition metal precursor is arc-discharged, nitrogen (N) and a transition metal may be evenly dispersed at the level of a single atom on the generated carbon support.
The single-atom catalyst supported on the carbon support manufactured by the method above may include a carbon support and a single-atom catalyst dispersed on the support.
The single-atom catalyst refers to a catalyst in the form that a single atom, which is the smallest in size that a catalyst material has, is dispersed on a support. The single-atom catalyst supported on the carbon support is characterized in that a catalyst material containing a hetero element other than carbon is evenly dispersed at the level of a single atom on a carbon support having excellent electrical conductivity. The characteristics allow the single-atom catalyst supported on the carbon support to have excellent electrical conductivity compared to a conventional nano-sized catalyst, and to have excellent catalytic activity and selectivity.
The carbon support refers to a carbon-based material having a large specific surface area and high crystallinity. For example, the carbon support may include graphene, graphene oxide, fullerene, carbon nanotubes (CNT), carbon nanofibers, carbon nanobelts, carbon nanoonions, carbon nanohorns, activated carbon, graphite, etc., but is not necessarily limited thereto, and any carbon supports that may be used as a carbon support in the art are all applicable.
The carbon support may have a structure such as a spherical shape, a rod shape, a tube shape, a horn shape, and a plate shape, but is not necessarily limited to such structures, and any structures that may be used as a carbon support in the art are all applicable. For example, the carbon support may be a porous carbon material having a large specific surface area and pores.
According to an embodiment, the carbon support is a nanohorn having a horn-shaped structure.
The carbon support may be porous. For example, the carbon support may be mesoporous. For example, in the carbon support, some or all of the various types of carbon supports described above may be porous.
The carbon support may have an average diameter of about 1 nm to about 10 μm. For example, the carbon support may have an average diameter of about 10 nm to about 5 μm. For example, the carbon support may have an average diameter of about 100 nm to about 1 μm. For example, the carbon support may have an average diameter of about 200 nm to about 500 nm. When the carbon support has an average diameter within the above range, the catalyst may be evenly dispersed in the form of a single atom on the carbon support, and catalytic activity and selectivity are excellent.
The term “single-atom catalyst” indicates that a catalyst material is dispersed as single-atom units together and evenly supported on a carbon support, and the single-atom catalyst is distinct from nanoparticles or microparticles formed of agglomerated catalyst materials, which are supported on a carbon support. The catalyst material is dispersed as single atom units together on a carbon support, and thus, the catalyst has excellent activity and selectivity.
The single-atom catalyst may include all hetero elements other than carbon. For example, the single-atom catalyst may include a non-metal, a metal other than carbon, or a combination thereof. For example, the single-atom catalyst may include at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); a transition metal; or a combination thereof. For example, the single-atom catalyst may include at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); at least one transition metal selected from cobalt (Co), iron (Fe), nickel (Ni), rhodium (Rh), and iridium (Ir); or a combination thereof. For example, the single-atom catalyst may include nitrogen (N), cobalt (Co), or a combination thereof. For example, the single-atom catalyst may include nitrogen (N) and cobalt (Co) together. For example, the single-atom catalyst may include nitrogen (N) or cobalt (Co).
The supported amount of the single-atom catalyst may be about 0.01% by weight to about 10% by weight with respect to the total weight of the carbon support. For example, the supported amount of the single-atom catalyst may be about 0.05% by weight to about 8% by weight with respect to the total weight of the carbon support. For example, the supported amount of the single-atom catalyst may be about 1% by weight to about 5% by weight with respect to the total weight of the carbon support. For example, the supported amount of the single-atom catalyst may be about 2% by weight to about 4% by weight with respect to the total weight of the carbon support. When the supported amount of the single-atom catalyst is within the above range, the catalyst may be evenly dispersed in the form of a single atom on the carbon support, and catalytic activity and selectivity are excellent.
The single-atom catalyst supported on the carbon support has excellent electrical conductivity and excellent catalytic activity and selectivity, and accordingly, the single-atom catalyst may be used in electrochemical or chemical reaction fields where conventional nano-sized or micro-sized catalysts are not applicable or hard to be applicable. For example, the single-atom catalyst may be used for fuel cells, highly sensitive biosensors, or chemical conversion reactions.
The disclosure will be explained in more detail referring to examples and comparative examples hereinafter. However, the examples are for illustrating the disclosure, and the scope of the disclosure is not limited thereto.
(Manufacturing of Carbon Nanohorn Structure Having a Single Atom Supported Therein)
100 g of graphite powder was washed with ethanol and dried in an oven at 50° C. for 2 hours to completely evaporate a solvent, and then the resultant was fully filled into a cylindrical negative electrode with an empty center and sufficiently dried in an oven to remove moisture.
For are discharge, the negative electrode was introduced into a reaction chamber, and the chamber was charged with a nitrogen atmosphere, and then a voltage of 30 V and a current of 150 A were applied thereto for 5 minutes to generate an intense arc. The product was cooled and washed with ethanol to manufacture a carbon structure doped with nitrogen (N).
0.1 g of CoCl2 was mixed with ethanol, and then 100 g of graphite powder was added to the mixture and stirred. Thereafter, the mixed solution was dried in an oven at 50° C. for 2 hours to completely evaporate the solvent to manufacture composite powder having CoCl2 adsorbed on a surface of the graphite. The obtained composite powder was fully filled in a cylindrical negative electrode with an empty center, and then sufficiently dried in an oven to remove moisture.
For are discharge, the negative electrode was introduced into a reaction chamber, and the chamber was charged with a nitrogen atmosphere, and then a voltage of 30 V and a current of 150 A were applied thereto for 5 minutes to generate an intense arc. The product was cooled and washed with ethanol to manufacture a carbon structure doped with cobalt (Co) and nitrogen (N) together.
A carbon structure doped with cobalt (Co) was manufactured in the same manner as in Example 2, except that a hydrogen atmosphere was applied instead of a nitrogen atmosphere.
A carbon structure doped with iron (Fe) was manufactured in the same manner as in Example 2, except that a hydrogen atmosphere was applied instead of a nitrogen atmosphere, and FeCl2 was used instead of CoCl2.
A carbon structure doped with nickel (Ni) was manufactured in the same manner as in Example 2, except that a hydrogen atmosphere was applied instead of a nitrogen atmosphere, and NiCl2 was used instead of COCl2.
A carbon structure doped with rhodium (Rh) was manufactured in the same manner as in Example 2, except that a hydrogen atmosphere was applied instead of a nitrogen atmosphere, and RhCl2 was used instead of CoCl2.
A carbon structure doped with iridium (Ir) was manufactured in the same manner as in Example 2, except that a hydrogen atmosphere was applied instead of a nitrogen atmosphere, and IrCl2 was used instead of CoCl2.
A carbon structure doped with boron (B) was manufactured in the same manner as in Example 1, except that a boron atmosphere was applied instead of a nitrogen atmosphere.
A carbon structure doped with sulfur (S) was manufactured in the same manner as in Example 1, except that a sulfur atmosphere was applied instead of a nitrogen atmosphere.
A carbon structure doped with phosphorus (P) was manufactured in the same manner as in Example 1, except that a phosphorus atmosphere was applied instead of a nitrogen atmosphere.
A carbon structure doped with nickel (Ni) and boron (B) together was manufactured in the same manner as in Example 2, except that a boron atmosphere was applied instead of a nitrogen atmosphere, and NiCl2 was used instead of CoCl2.
A carbon structure doped with cobalt (Co), nickel (Ni) and nitrogen (N) together was manufactured in the same manner as in Example 2, except that a mixture of CoCl2 and NiCl2 was used instead of CoCl2.
X-ray diffraction (XRD) analysis was performed on the carbon structure doped with nitrogen (N) of Example 1 and the carbon structure doped with cobalt (Co) and nitrogen (N) together of Example 2, and the results are shown in FIG. 1 .
As shown in FIG. 1 , the XRD results of the carbon structures of Examples 1 and 2 showed a sharp 2θ diffraction peak at about 25°, indicating that the carbon structure was a crystalline structure. However, no peaks resulting from nitrogen (N) and cobalt (Co) were observed, indicating that nitrogen (N) and cobalt (Co) each were doped to the carbon structure at the level of a single atom rather than a large nanoparticle.
Scanning electron microscopy (SEM) analysis was performed on the carbon structure doped with nitrogen (N) of Example 1 and the carbon structure doped with cobalt (Co) and nitrogen (N) together of Example 2, and the results are respectively shown in FIGS. 2 (a) and (b) .
In addition, transmission electron microscopy (TEM) analysis was performed on the carbon structure doped with nitrogen (N) of Example 1 and the carbon structure doped with cobalt (Co) and nitrogen (N) together of Example 2, and the results are shown in FIG. 3 .
As shown in FIG. 2 , both the carbon structure doped with nitrogen (N) and the carbon structure doped with cobalt (Co) and nitrogen (N) together exhibited a shape of a spherical carbon nanohorn having a constant shape and size. In addition, it was found that even in the structure of an atom-doped carbon nanohorn, a uniform spherical shape is well maintained without any specific changes in shape.
As shown in FIG. 3 , similar to the results of scanning electron microscopy (SEM), both the carbon structure doped with nitrogen (N) and the carbon structure doped with cobalt (Co) and nitrogen (N) together exhibited a shape of a spherical carbon nanohorn having a constant shape and size. When viewed through transmission electron microscopy (TEM), it was found that the carbon nanohorn shape was well formed, and at low magnification, specific metal particles characteristics were not found, but when viewed at high magnification, particles having metallic characteristics were found to be dispersed at the level of an atom. In addition, it was found that the carbon nanohorn had an average diameter of about 20 nm to about 50 nm.
From the SEM and TEM results above, it was found that the doping of nitrogen (N) and cobalt (Co) does not affect the nanohorn shape of the carbon structure, indicating that nitrogen (N) and cobalt (Co) each were doped to the carbon structure at the level of a single atom rather than a large nanoparticle.
An experiment was performed to find out the amount of a cobalt metal precursor and optimal conditions for ammonia heat treatment. Composite powder having different amounts of CoCl2 adsorbed on a surface of graphite was manufactured by applying different amounts of a metal precursor mixed with graphite from low to high concentrations. The obtained composite powder was filled in a cylindrical negative electrode with an empty center, and then dried in an oven to remove moisture.
For are discharge, the negative electrode was introduced into a reaction chamber, and the chamber was charged with a nitrogen atmosphere, and then a voltage of 30 V and a current of 150 A were applied thereto for 5 minutes to generate an intense arc. The product was cooled and washed with ethanol to manufacture a carbon structure doped with various amounts of cobalt (Co) and nitrogen (N) together.
In addition, in order to create a stable and active coordination structure, heat treatment using ammonia was performed, and in this case, a catalyst having an optimal oxygen reduction reaction activity was synthesized by varying heat treatment temperatures.
X-ray photoelectron spectroscopy (XPS) analysis was performed to examine binding properties of cobalt for the carbon structure doped with cobalt and nitrogen together of Example 13, and the results are shown in FIG. 4 . As shown in FIG. 4 , it was found that, with an increase in the amount of the cobalt element, Co—N bonds were observed, indicating that more bonds between cobalt and nitrogen were generated.
In addition, the XPS analysis results according to the ammonia heat treatment and temperature are shown in FIG. 5 . As shown in FIG. 5 , with no ammonia heat treatment or at low temperature, more bonds between cobalt and oxygen were observed, whereas at high temperature, more bonds between cobalt and nitrogen were observed, indicating that a single atom of cobalt coordinates with nitrogen.
For the carbon structure doped with cobalt and nitrogen together of Example 13, linear sweep voltammetry (LSV) measurement was performed, and the results are shown in FIGS. 6A to 6C . As shown in FIGS. 6A to 6C , when cobalt was included, changes in reduction characteristics were found, indicating that cobalt was serving as a catalyst, and when oxygen reduction reaction was performed, cobalt was found to have high performance almost similar to a commercially available Pt catalyst.
Meanwhile, FIG. 7 shows a graph of the LSV results of measuring catalytic activity changes according to the amount of a cobalt element. As shown in FIG. 7 , with an increase in the amount of cobalt, single-atom catalyst points increase and thus, the activity increases, but when the amount of cobalt increases by more than a certain amount, the activity decreases due to aggregation.
While exemplary embodiments according to the disclosure have been shown and described with reference to drawings and examples, this is intended to be illustrative, and it will be understood by those of ordinary skill in the art that various modifications and equivalent arrangements may be made therein. Hence, the protective scope of the disclosure shall be determined by the scope of the appended claims.
According to an aspect, a method for manufacturing a single-atom catalyst supported on a carbon support, through a bottom-up approach, introduces a single-atom catalyst material into a carbon lattice when generating a carbon support, thereby manufacturing a single-atom catalyst supported on a carbon support having high crystallinity and a large specific surface area.
The single-atom catalyst supported on the carbon support has excellent electrical conductivity, and has excellent catalytic activity and selectivity as the single-atom catalyst is evenly dispersed on the carbon support.
Claims (21)
1. A method for manufacturing a single-atom catalyst supported on a precursor formed carbon support, the method comprising:
treating a mixture of a precursor including carbon and a precursor of a hetero element other than carbon in a dry vapor phase process to provide a single-atom catalyst containing a hetero element other than carbon,
wherein the single-atom catalyst is positioned on the precursor formed carbon support from the precursor including carbon during the dry vapor phase process,
wherein the precursor formed carbon support comprises at least one of graphene, graphene oxide, fullerene, carbon nanotubes (CNT), carbon nanofibers, carbon nanobelts, carbon nanoonions, or carbon nanohorns.
2. The method of claim 1 , wherein the precursor including carbon comprises at least one selected from graphite, C2H2, CH4, C2H4, C2H6, or C2H5OH.
3. The method of claim 1 , wherein the precursor of a hetero element other than carbon comprises: at least one non-metal-containing precursor including at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), or iodine (I); at least one metal-containing precursor including at least one metal selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, La, Zr, Hf, Nb, Ta, Mo, W, Tc, Re, Ru, Os, Rh, Ir, Pd, of Pt, Ag, Au, Cd, Hg, Ga, Ge, In, Sn, Sb, Tl, Pb, Bi, a lanthanide metal, or an actinide metal; or a combination thereof.
4. The method of claim 3 , wherein the at least one non-metal-containing precursor is a nitrogen-containing precursor comprising at least one of N2, NH3, N2H4, RxNH3-x (R is a C1 to C6 alkyl group, and x is 1 or 2), RxN2H4-x (R is a C1 to C6 alkyl group, and x is an integer of 3 or less), a solid inorganic material containing a nitrogen element, or a nitrogen element-containing polymer.
5. The method of claim 3 , wherein the metal-containing precursor comprises at least one of CoCl2, CoBr2, Co(NO3)2, Co(OH)2, Co(CH3COO)2, FeCl2, FeBr2, Fe(NO3)2, Fe(OH)2, Fe(CH3COO)2, NiCl2, NiBr2, Ni(NO3)2, Ni(OH)2, Ni(CH3COO)2, RhCl2, RhBr2, Rh(NO3)2, Rh(OH)2, Rh(CH3COO)2, IrCl2, IrBr2, Ir(NO3)2, Ir(OH)2, or Ir(CH3COO)2.
6. The method of claim 1 , wherein the precursor of a hetero element other than carbon comprises: at least one non-metal-containing precursor including at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), or phosphorus (P); at least one metal-containing precursor including at least one metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Ru, Rh, Ir, Pd, Pt, Ag, Au, Cd, Ga, Ge, In, Sn, Sb, or Tl; or a combination thereof.
7. The method of claim 1 , wherein the precursor of a hetero element other than carbon comprises: at least one non-metal-containing precursor containing at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), or phosphorus (P); at least one metal-containing precursor containing at least one metal selected from Co, Fe, Ni, Rh, or Ir; or a combination thereof.
8. The method of claim 1 , wherein the amount of the precursor of a hetero element other than carbon in the mixture is about 0.01% by weight to about 10% by weight with respect to the total weight of the precursor including carbon.
9. The method of claim 1 , wherein the dry vapor phase process is performed through at least one process among arc discharge, thermal chemical vapor deposition, plasma synthesis, high-temperature plasma, plasma-enhanced chemical vapor deposition, laser evaporation, laser ablation, and vapor phase growth.
10. The method of claim 1 , wherein the dry vapor phase process is performed through arc discharge at a voltage of about 10 V to about 100 V and a current of about 10 A to about 300 A.
11. The method of claim 1 , wherein the precursor formed carbon support has at least one structure selected from a spherical shape, a rod shape, a tube shape, a horn shape, or a plate shape.
12. The method of claim 1 , wherein the precursor formed carbon support has a horn-shaped structure.
13. The method of claim 1 , wherein the precursor formed carbon support has an average diameter of about 1 nm to about 10 μm.
14. The method of claim 1 , wherein the hetero element other than carbon comprises: at least one non-metal selected from nitrogen (N), boron (B), sulfur (S), selenium (Se), phosphorus (P), fluorine (F), chlorine (Cl), bromine (Br), or iodine (I); at least one metal selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, La, Zr, Hf, Nb, Ta, Mo, W, Tc, Re, Ru, Os, Rh, Ir, Pd, of Pt, Ag, Au, Cd, Hg, Ga, Ge, In, Sn, Sb, TI, Pb, Bi, a lanthanide metal, or an actinide metal; or a combination thereof.
15. The method of claim 14 , wherein the metal comprises at least one of cobalt (Co), iron (Fe), nickel (Ni), rhodium (Rh), or iridium (Ir).
16. The method of claim 1 , wherein the hetero element other than carbon comprises nitrogen (N), cobalt (Co), or a combination thereof.
17. The method of claim 1 , wherein the supported amount of the single-atom catalyst is about 0.01% by weight to about 10% by weight with respect to the total weight of the precursor formed carbon support.
18. The method of claim 1 , wherein the single-atom catalyst is an electrochemical catalyst.
19. A single-atom catalyst supported on the precursor formed carbon support manufactured through the manufacturing method according to claim 1 .
20. The method of claim 1 , wherein the single-atom catalyst is a chemical reaction catalyst.
21. A method for manufacturing a single-atom catalyst supported on a carbon support, the method comprising treating a mixture of a precursor including carbon and a precursor of a hetero element other than carbon in an arc discharge process to provide a single-atom catalyst containing a hetero element other than carbon on a carbon support;
wherein the arc discharge process is conducted at a voltage of about 10 V to about 100 V and a current of about 10 A to about 300 A.
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| PCT/KR2019/014958 WO2020096338A1 (en) | 2018-11-08 | 2019-11-06 | Method for preparing single-atom catalyst supported on carbon support |
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| Korean Notice of Allowance for KR Application No. 10-2018-0136808 dated Oct. 23, 2020. |
| Korean Office Action for KR Application No. 10-2018-0136808 dated Feb. 27, 2020. |
Also Published As
| Publication number | Publication date |
|---|---|
| US20210394161A1 (en) | 2021-12-23 |
| KR20200053323A (en) | 2020-05-18 |
| KR102182553B1 (en) | 2020-11-24 |
| WO2020096338A1 (en) | 2020-05-14 |
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